Hydrochloric Acid → HCID 178486309、化合物

HRID 487336

反応式

HRID 487336 の反応式
[CH:1]1[C:12]([OH:13])=[C:11]2[C:4]([C:5]([CH:7]=[CH:8][C:9]2=[O:10])=[O:6])=[C:3]([OH:14])[CH:2]=1.[OH-].[Na+].Cl.[C:18]([O:21][CH2:22][CH3:23])(=O)C>C(Cl)Cl.O.CCCCCC>[OH:14][C:3]1[CH:2]=[CH:1][C:12]([OH:13])=[C:11]2[C:4]=1[C:5](=[O:6])[C:7]1[CH:2]3[CH2:3][CH2:23][C:22]([O:21][CH3:18])([C:8]=1[C:9]2=[O:10])[CH:12]=[CH:1]3

参加物

8

反応物 4

HCID 313Hydrochloric AcidHCID 8857Ethyl Acetate2 回HCID 10141NaphthazarinHCID 14798Sodium Hydroxide

生成物 1

HCID 178486309HCID 178486309、化合物収率 83%

試薬・触媒・溶媒 3

HCID 962Water溶媒HCID 6344Dichloromethane溶媒HCID 8058Hexane溶媒2 回

反応条件

温度
0 °C

実験手順

20.9 g (0.11 mol) of naphthazarin (8) and 28.4 g of 1-methoxy-1,3-chclohexadiene (19) (technical grade, 70%, 0.177 mol) were refluxed in 330 ml of methylene chloride (temperature oil bath 50° C.). The course of the reaction was followed by means of TLC (ethyl acetate:n-hexane, 2:5). After evaporation 330 ml of pentane was added to the residue and the solution was stirred for 5 minutes. The solution was cooled to 0° C. and filtrated. The filtrate was rinsed with 2×50 ml of petroleum ether. The yield of the yellow/brown product was 30.0 g (91%). The crystals were taken up in a solution of 22.0 g (0.55 mol) of caustic soda in 825 ml of water. During half an hour air was passed through the solution while the solution was stirred. The colour of the solution changed from green to blue. The course of the reaction was followed by means of TLC (ethyl acetate:n-hexane, 2:5). After the reaction 46.2 ml of concentrated HCl (37%) was added to the solution. The product precipitated as a red solid which was filtered off. This compound was dried on a film evaporator (2 mm Hg) and in a vacuum dessicator (over P2O5) during at least one night. The yield of the red compound (20) was 27.0 g (91%). The overall yield was 83%. Melting point 239°-241° C. 1H-NMR (90 MHz, CDCl3, TMS internal standard): δ=1.39-1.92 ppm (4H, m, CH2 --CH2), δ=3,69 ppm (3H, s, OMe), δ=4,53 ppm (1H, m, H4), δ=6.40 ppm (1H, dd, J=5.6 Hz and J=8 Hz), δ=6.64 ppm (1H, dd, J=8 Hz and J=1.5 Hz), δ=7.12 ppm (2H, s, ArH), δ=12.60 ppm (1H, s, ArOH), δ=13.06 ppm (1H, s, ArOH).

後処理

  1. customAfter evaporation 330 ml of pentane
  2. additionwas added to the residue
  3. filtrationfiltrated
  4. washThe filtrate was rinsed with 2×50 ml of petroleum ether
  5. waitDuring half an hour air was passed through the solution while the solution
  6. stirringwas stirred
  7. additionwas added to the solution
  8. customThe product precipitated as a red solid which
  9. filtrationwas filtered off
  10. dry with materialThis compound was dried on a film evaporator (2 mm Hg) and in a vacuum dessicator (over P2O5) during at least one night

出典と根拠

ORDレコード
ord-5f331550d5a04a31b38de2615447d068
出典データセット
uspto-grants-1994_03
特許番号
US05294701

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